1-nitro-anthraquinonyl-6-amino compounds and their production



Putented June 16,1936 1 t 1-NITRO-ANTHRAQUINONYL-6-AMINO COM- POUNDS ANDTHEIR. PRODUCTION Earl Edson Beard, Milwaukee, Wis., assignorto E. I. duPont de Nemours & Company, Wilmington, DcL, aeorporation of Delaware NoDrawing. Application May 18, 1935,

Serial No. 22,176 I 11 Claims. (01.260 21) This invention relates tocarbon, compounds Specifically one method of carrying out the .andprocesses for their production. Moreparinvention is to treatl-nitro-anthraquinone-G- ticularly it relates to dye intermediates, dyescarboxylic acid in such away as to produce a and. colored compounds ofthe 'anthraquinone' 1-nltro-anthraquinone-6-carbonylhalide and ;5series. It especially contemplates anthraquinone thereafter condense theresultant compound with 5 derivatives having the probable formula; aheterocyclic amine having at least one hydrogen atom attached to theamine nitrogen atom.

I v The invention will be further understood from 0=N 0 I aconsideration of the following detailed descrip- IT D STATES PATENT OFFIll tion and specific examples in which the parts 10 are given by weight.

Pmam'rron or l -Nrmo-Anrnaaqmnonn-ii-Caa- I II A BONYL Hmnas a, 0

Z representing a heterocyclic carbon compound radical, residue ornucleus, and the production of such compounds froml-nitro-anthraquinoneo G-carboxylic acid.

Example I I Ten (10)' parts of l-nitro-anthraquinone-G carboxylic acidwere suspended in 100 parts of benzene. Ten (10) parts of phosphoruspentachloride were added to the sus nsion and the The production ofl-nitro-anthraqumo whole heated at 80 C. for one l iour. The recarboxyhcand 15 described by Eckert (1914 action mixture was then cooled to 15 C.and' Monats. fur Chemie 35 289), by Beard 8: Lulek filtered The cake orthe acid chloride was (U. S. Patent 1,991,191, Feb. 12, 1935) and by.washed'with benzene and dried Beard (U. S. Patent 1,985,232, Dec.25,1934). 1 25 I This application is in the natureof a com Theconversion of the acid to the carbonyl -tinuation-in-part of -my garlierapplication Ser. 23 :2 3? gz ig gi gggfi g xa g zggz g -N0. 590,640,filed Feb. 3, 1 32, U. S. Patent 2,001,- 701 issued May 21, 1935. In theearlier applicabenzene, -b fh tion the symbol Z in the generalstructural iorbenzene and the tri'cmoro benzenes 9 suitable 30 mulacovered aliphatic, carbocyclic and heteromi tures of the compoundslisted; and at other cyclic nuclei. Inthis application the samesymtemperatures depending p h Particular bol is used to represent a morelimited field, 8 m usednamely, heterocyclic nuclei. Good results arealso obtainable with'solvent invention has for an object theproducnaphtha as a suspension agent. Particular'men- 35 tion of new andvaluable, chemical compounds. tion may be made of thionyl chloride as anagent Other objects are to produce new dyes, new dye for the conversionto the desired compound. intermediates, new vat colors, new color subfla y particular Carbonyl halide y b stances, new colored compounds, toproducesuch produced, p cial y good results a e obtainable 4 products bynew chemical processes and in a in. the case of the chloride and thebromide. It 40 "very desirable state of purity and physical form.desired, the phosphorus penta-halide may be A general advance in,,theart and other obprepared in the solvent to be used later for the jectswhich will appear hereinafter are also conconversion oi the carboxylicacid to carbonyl templated. halide. This may be accomplished, forexample, The foregoing objects and related ends are acby addingphosphorus tri-chloride'to the solvent complished in a manner set out inthe following and then passing a stream of chlorine gas .description inwhich details of what believed throu'ghthe solution until thetheoreticalamount to be the best mode for carrying out the invenhas beenadded or absorbed according to the so tion are disclosed. I l equation:

PREPARATION or l-Nrrao-Anrnaaqmuonn-G-Acn.

" Ammo Couronnns -7 Example II Ten (10) parts ofl-nitro-anthraquinone-ficarbonyl ,chloride were condensed with 6.2 partsof beta-amino-phenazine, utilizing 150 parts of chlorobenzene as asolvent medium. After heating the reactants at 125-135 C. for 1 hour themass was cooled to 75 C. and filtered.

In a similar manner, l-nitro-anthraquinone- G-carbonyl halides may becondensed with such compounds as 2amino-phenanthridone,21-amino-diphenylene-oxide, 4-amino-acridone, t-amino-thioxanthone,3-arnino-carbazole, 2,2' diamino-diphenylene-sulfide, 1,3 di-aminophenoxthin and 2,7-di-amino-xanthone.

I Example HI Ten (10) parts of l-nitro-anthraquinone-ficarbonyl chlorideand 10.7 parts of 5'-aminoanthraquinonyl-l (N) -2 (N) -2' (C)-phenyl-imida- I zole were mixed and agitated with 200 parts ofnitrobenzene at 150 C. during 1 to 2 hours. Thereafter the reaction masswas cooled to 40 C. and the resultant dye separated by filtration.

Example IV Ten (10) parts of l-nitro-anthraquinone iicarbonyl chlorideand 5 parts of para-aminophenyl morpholine were mixed and agitated at50-70 C. After one hour, dilute hydrochloric acid was added to take upany remaining paraamino-phenyl morpholine and the 1 -nitro-anphenylthraquinone 6 carbonyl 4' amino 'morpholine removed by filtration.

In a similar manner, I-nitrO-anthra uin'one- G-c'arbonyl halides may becondensed with such compounds as 5-amino-8-ethoxy-quinoline, pi-

peridine, di-amino-di-naphthalene-doxide, tetrahydro-'alpha-furfurylamine, di-alpha-fUrfuryl amine, perimidone, 3,6-di' amino-fluoran and4,4-di-amino-indanthrone.

Example V -I'hirty-five (35) parts of l-nitro-anthraquinone-G-carbonylchloride and 20 parts of paraamino-phenyl-.(N)-morpholine were mixed andagitated in 500 parts of nitrobenzene at 140 C.-

Example VI 0 Ten 10) parts of 1-nitro-anthraquinone-6-. carbonylchloride-and 1 parts of 1,9-pyrazol-anthrone were heated together in 150parts of ortho dichloroberlzene' at 160 C. for 2 hours. The condensationproduct was filtered off at C. and

- washed with'ortho-di-chlorobenzene and alcohol.

This process gives a product which dissolves in sulfuric acid, ,coloringthe resultant solution yellow to orange. The product vats from analkaline hydrosulfite vat as a red-brown solution.

"EzampleVII' Ten (10) parts ofl-nitro-anthraquinone-B- carboxylic acidchloride and 8 parts of 1,9-

anthraisothiazole-a-an ine were-heated together it to 1 hour, thereaftercooled to 70 C. The 75 r brown colored.

in 250 parts of nitrobenzene at 150 C. for two and one-half hours. Theresultant product was isolated by filtration at C. and washed withnitrobenzene and alcohol, and thereafter-dried.

' The product gives ayellow to orange color in sulfuric acid. Itsalkaline hydrosulfite vat is red- Example vlzr Ten (10)* parts of1-nitro-anthraquinone-6-' carbonyl chloride and 7 parts of1,9-pyrazolanthrone were heated together in 150 parts of nitrobenzene at160-165 C. for 2 hours. The condensation product was-filtered off at 70C. and washed with nitrobenzene and alcohol. process gives a productwhich dissolves in sulfuric acid, coloring the resultant solution yellowto orangeandvats as a reddish-brown solution.

Example IX Teri (10) parts of l-nitroranthraquinone-6- carboxylic acidchloride and 8 parts of 1,9-anthraisoseEenazole-5-amine were heatedtogether in 200 parts of nitrobenzene at 150 C. for two hours. Theresultant product was filtered off at 80 C. and washed with nitrobenzeneand alcohol, and thereafter dried. The product gives a yellow to orangecolor in sulfuric acid and a red-brown colored alkaline hydrosulfitevat.

Example XI I F'fty .(50) parts of'l-nitro-anthraquinone ficarbonylchloride and 40 parts of 1,9-anthraisothiazolei-amine were mixedtogether and agitated in 1000 parts of nitrobenzene at C. during 2 hoursand thereafter isolated according to the procedure given in Example X.

Example XII This 1 C. during 2 hours and thereafter isolated accordingto the procedure given in Example X.

Example XIII Fifty '(50) parts of I-nitro-anthraquinone-6-- carbonylchloride and 40 parts of 1,9-anthra- Y isothiazole-2-amine weremixed'and agitated in 800 parts of trichlorobenzene at 150 C. during 1-2hours and thereafter cooled and'flltered.

' Erample XIV Fifty (50) parts of 1-nitro-anthraquinone-6- carbonylchloride and 40 parts of 1,9-anthrathiophene-2-amine were mixed andagitated'in 800 parts of. trichlorobenzene at 150 C. during 1-2, hours,thereafter cooled and filtered.

Example xv Twenty-five-(25) parts of l-nitro-anthraqui- 70 2,043,995condensation product which separates out in yellow crystals was filteredoi! and washed as described in the'preceding examples.

. Example xv!"- Twenty-flye 25) parts of1-nitro-an'thraquinone-6-carbonylchloride and 37 parts of 5.'-amino-1(S) -2,2'-di-anthraquinonyl-thiazole w e r e mixed and heated at 160 C.111-800-1000 parts ot'nitrobenzene during 1-2 hours. The reaction 'rnasswas then cooled to 100 C. and filtered to 4 isolate-the resulting dye.

This compound probably has the formula:

0 i ll about 2 hours.

, Example XVII 1 Ten (10) parts of l-nltro-anthraquinone-ficarbonylchloride and 12.7 parts of5-ethoxy-phenyl4,2,2'-anthraquinonyi-thiazo1e-5'-amine were during 2hours. The reaction mass-was cooled to 40 C. and the dye obtainedseparated by filtration.

' Example XIX A Ten (10) parts oi 1-nitro-anthraquinone-6- carbonylchloride were condensed with 37 partsof 1'-amino-1 (S) 2,2f-di-anthraquinonyl-thiazole -in 900 parts oi'nitrobenzenewhile heatingat 160 C. The heating was continued for 2 hours after whichthe reactionmass was cooled to .100 C. and filtered;

The product obtained'probably has the tollowing formula: v

I mannersimilar to that described in Example XX Y Ten 10) parts oi!1-nitro-anthraquinone-6- carbonyl chloride were condensed with 17 partsof 1 (Se) 2,2'-di anthraquinonyl selenazole 5'- amine in 850-950parts'ot nitrobenzene while heating at -165 C. The heating was continuedfor about 2 hours, after which time the reaction mass was cooled to 100C. and filtered -in order to isolate the desired dyestufl.

Example XXI Ten (10) parts of l-nitro-anthraquinone-ficarbonyl chloridewere condensed with 17 parts of 1,2,2di-anthraquinonyl-se1enazole-1'-amine in a the preceding example.

' Example XXII Ten (10) parts (2 mois) oil-nitro-a-nthraquinone-B-carbonyl chloride and 7.2 parts (1 mol) of4,4'-diamino-i,1-di-anthrimide carbazole were mixed and agitated in300-400 parts of nitrobenzene, at -180 0. during 24 hours. The reactionmass was then cooled to 80 C. and filtered,

thereafter ,washed with nitrobenzene and alcohol. anddried.

Example XXIII Ten (10) parts (2 mols) ofl-nitro-anthraquinone-6-carbonyl chloride and 7.2 parts (1 mol) of5,5-diamino LIGdi-anthrimide car 1e were mixed and agitated in 300-500parts 01' nitrobenzene at 160-180 C. during 2-4 hours. The reac- Vtionmass is then cooled to 80. C. and filtered,

thereaiter washed with nitrobenzene and alcohol. and dried.

Example XXI V Ten-(10) parts (2 mols) ofl-nitro-anthraquinone-6-carbonyl chloride and 7.2 parts (1 mol) of4,5'-dia1 nlno 1,1'-di-anthrimide' carbazole are mixed and agitated in300-500 parts of nitrobenzene at 160-180 C. during 2-4 hours. -Thereaction mass is then cooledto 80 C. and filtered,

thereafter washed with nitrobenz ene and alcohol, and dried.

I Example XXV Ten 10)",parts (1 moi) of.l-nitro-anthraquinone-6.-carbonyl chloride and 14.4 parts (1 mol) of4,4'-di-amino-1,1' di anthrimide carbazole were condensed in 300-400parts ofnitrobenzene, care being takento add the acid chloride slowly tothesuspension media containing the di-aminocarbazole compound, over aperiod of 1 hour while 'maintalning the temperature at 200-215 C.

Thereafter, the temperature was allowed to fall to 70 C. during a periodof about 2 hours after which time themono-acidylated compound wasfiltered ofl.

Example XXVI Ten (10) parts of l-nitro-anthraquinone-G- carbonylchloride and 22 parts of the amine prepared by hydrolysis of thecarbazolized condensation product ofl-benzoylamino-5-chloro-anthraquinorie and 5'-amino-1'(S)2,2'-dianthraquinonyl thiazolc, were condensed'in 500 parts ofnitrobenzene at C. during 2-3 hours. Thereafter the reaction massiscooled to 80-100 C. and filtered.

This resultant dye probably has followingiormula: 1 g

' or 1(N-methyl)-9- anthra-pyridone-4-amine -in p El'cample xxvn I Ten(10) parts of l-nitro-anthraquinone-6- carbonyl chloride and 14 parts of'-5'-amino-1,1'-

di-anthrlmide carbazole (prepared by hydrolysis ,of.5-benzoylamino-1,1'-di-anthrimide carbazoie disclosed in Example 6 ofGerman Patent 566,708, and Example 6 of French Patent 711,433,) were,mixed and'agitated in 300 parts of nitrobenzene at 160-180 C. during-24hours. The reaction mass was then cooled to-100 C. and filtered. The dyeobtained probably has the following for- Example xxvm f Ten (10) partsof l-nitro-arithraquinone-B- carbonyl chloride'and 11 parts ofmono-amino- 1(S) 2(N) -anthraquinonyl -(C) phenyl thiazole.

(prepared by reduction of the mono-nitration product of1(S)2(N)-anthraquinonyl-(C) -ph'em'l thiazole) were mixed with 300 partsof nitrobenzene and heated with agitation to 1609-180 C. during 2-3hours. Thereafter the dyestui! was isolated by filtration. I

a le xxix Ten (10) parts of I-nitro-anthraquinOne-G- I carbonyl chloridewere condensed with 8.7 parts 200 parts of nitrobenzene while at art.

C. for a period of 2 hours. "The dye obtained was isolated byfiltration, after cooling to 80 C.

Example xxx Ten 10) parts of 1-nitro-anthraquinone-6- carbonyl chloridewere condensed with 8.7 parts of 1(N-methyl)-9-anthra-pyridone-5-aminein 200 parts of nitrobenzene while heating at 140- 150 C. for a periodof 2 hours. The dye obtained was isolated by filtration, after coolingto 60 C.

Example XXX! The nitro g'roup in the product obtained according to.Example XXIX was reduced by vatting the compound in alkaline sodiumhydrosulflte accordingto procedures well known in the dyestufi The aminobody was then isolated and 16.7 parts of same were condensed with 10parts of 1-nitro-anthraquinone-G-carbonyl chloride in 300-400 parts ofnitroben'zene while maintaining a temperature of 150-160 C. over aperiod of 2-3 hours. The resultant mass was cooled to 60 C. and thecondensation product isolated by filtration. I

a V Example XXXII The nitro group in the product obtained ac- .cordingto Example XXX was reduced by vatting the compound in sodiumhydrosulfite. amino body was then isolated and condensed (16.7 parts)with 1-nitro-anthraquinone-6-carbonyl chloride (10 parts) according tothe method outlined in Example XXXI.

- As will be apparent from the foregoing, the invention is not limitedto the particular amines utilized in the specific examples. It is ofgeneral character. However, certain amines merit special mention forexample:

1,9 anthraisothiazole-5-amine; having the formula:

I-lI-S I HIN. I v 1,9-anthraisothiazolei-amine,1,9-anthraisothiazole-2-amine, 1,9-anthraisothiazole-8ramine,1,9-anthraisoselenazole-4-amine, having formula:

the

1,9-anthraisoselenazole-2-amine, 1,9-anthraisoselenazole-a-amine,1,9-anthraisoselenazole-5-amine, Piperidine, having the iormula:

5-amino-8-ethoxy-quinoline, having the formula: NH"

-- 2,6-di-amino-diphenylene-oxide,

1,3-di-amino-diphenylene-d,ioxide,

3-amino-xanthone,

2,7-di-amino-xanthone, 7-nitro-2-amino-xanthone,

' 4-amino-alizarine-ethylene-ether,

3-amino-naphthalic' acid anhydride, 4-amino-L8-naphthalic acidethyl-imide, 4-amino-1,8-naphthalic acid-2'-methylphe-' nyl-imide,4-amino-L8-naphthalic acid methyl-imide.

4-amino-l,8-naphthalic acid phenyl-imide,

. 4-amino-l,8-naphthalic acid 2'-chloro-phe-' nyl-imide,

' 3,6-di-.am,ino-fluoran,

Mono-amino-acridone, Di-amino-acridone, 4-amino-6-nitro-quinazoline,6,6'edi-amino-4,4'-di-quinazolinyl-para-para'- di-amino-benzene,Perimidone, 4-amino-1,9(1 '-methyl) -anthrapyridone,

Y 5-amino-1,9(1'-ethyl) -anthrapyridone,

4-amino-Py-C-ethyl-LQ-anthrapyrimidine,5-amino-Py-C-phenyl-1,9-anthrapyrimidine,8-aminc-Py-C-butyl-1,9-anthrapyrimidine,4-amino-anthraquinone-2,i-phenyl-acridone,

' 5-amino anthraquinone-2,l-phenyl-acridone,

' 8-amino-anthraquinone-2,1-phenyl-acridone, 7,7'-di-amino-thioindigo, J5,5cli-chlor-'7,'7'-diramino-thioindigo,

' 5,5-di-amino-thioindigo, 6,6'-di-amino-thioindigo,n-Amino-iso-indigotine,

- 4 ,4'-di-amino-indanthrone,

Tetra-amino-di-hydroxy-flavanthrone, Y Anthraquinone-1(N)-naphthacrldone.

So far no heterocyclic carbon compound containing a free amino group hasbeen found that will not condense with 1-nitro-anthraquinone-6- carbonylchloride under the disclosed conditions.

- This is true even in cases where substituent radiesses hereindescribed and therefore it is not desired to limit the invention to thesame.

The particular temperatures and time utilized for the condensation of.the"1-nitro-anthra|qui-'- none-G-carbonyl chloride with thevarious'heter ocyclio amines depends upon the 'characteristics of theheterocyclic compound being treated.

.Temperatures higher than ordinary room or atvof the influence oftemperature upon the speed of the reaction. High yields are to someextent dependent upon preferred or selected temperature ranges which mayreadily be determined empirically. vSo far as now :appears, thecondensation may be carried out atany temperature up to thedecomposition point of the retime of reaction, a factor readilydeterminable empirically.-

As will be clear from the specific examples, the amount of solvent orsuspension media (if any) used for carrying out the condensation may bevaried over a wide range, depending largely upon the characteristics ofthe particular condensation and the convenience of the person carryingout the same. This fact is one readily determinable by those skilled inthe art.

Particular mention may be made of such reaction media as nitrobenzene,,the chloro-benzenes (particularly tri-chloro-benzene andortho-di-ehloro-benzene), the xylenes (for example commercial xylenemixtures), naphthalene. solvent naphtha and the like.

Throughout the specification and claims the term-vat color is used tocover compounds susceptible to. vatting by'any oi the methods known tothe art, (see Colour Index"). It includes vat, dyes and vattablecompounds which are not dyes.

The compounds produced by this invention are colored and are valuablefor the,purpose of coloring various substances. These materials are alsovaluable as intermediates for vat color and anthraquinone dyes.

As many apparently widely diiferent embodiments of this invention may bemade without departing from the spirit and-scope thereof, it is to beunderstood that I do not limit myself to the specific embodimentsthereof except as defined in the appended claims. 1

1. The process which comprises condensing a1-nitro-anthraquinone-6-carbonyl halide with a heterocyclic aminecontaining at least one hydrogen atom attached to the amine nitrogenatom.

2. The compound having the formula:

1-nitro-anthraquinone-B-carbonyl halide with a heterocyclic aminecontaining at least one hydrogen atom attached to the amine nitrogenatom, the said heterocyclic amine containing a pyrrol nucleus.

5. The process which comprises condensing a l-nitro-anthraquinone-6-carbonyl halide with a heterocyclic aminecontaining at least one hyactants or the final product. Obviously,temdrogen atom attached to the amine nitrogen obtainable by condensingl-nitro-anthraquinone B-carbonyl chloride with5'-amino-anthraquinone-1'-Bz-1-benzanthrone acridine.

10. The compound-having the formula:

o=il

-N-Z I i i Z representing a heterocyclic radical containing a pyridinenucleus. 7

7. The compound having the formula:

atom, the said heterocyclic amine containing an azole nucleus.

6. The compound having the formula:

Z representing a heterocyclic radical containing 1 a'pyrrol nucleus.

8- e p und having t e formula-i obtainable by condensing 1nitro-anthraquio none-B-carbonyl-chloride with '-amino-1,1'-dioanthrimide-carbazole.

l 11. The compound having the formula:

. o c-n-z 04$ 0 Z representing a heterocyclic radical containing anazole nucleus. 0 9. The compound having the formula: I

obtainable by condensing l-nitro-anthraqmnone- 6-carbonyl-chloride with5-amln0-1(S) -2,2'-dianthraquinoyl-thiazole.

' EARL EDSON BEARD.

. PatentNo. 2,043,9s5..-

Certificate of Correction EA unnnsonmn It'is hereby that mo appearinfthe printed specification-of theahovenumberedpetentrequiring-oorreetionas-followsr Ergo-:6,first column; line1'5;1in.-.the last anthraquinone nucleus of the formula, for V i 6&6

-' Egge 7, first eo1u1nn, 1ine.45vfor the numeral 6 read 6";page I2;firstroluinn, e 38, for n-Amin'o-iso-in tine read 5:5-di-amino-indzgo;and line 41;"for

Anthraquinone-l (N)-naphthaoridone read Mono-amino-flavanthrone; andthat the said Letters Patent should be read with these correctionstherein that the-same may.

conform to the record of the ease in the Patent Office. v

Signed and sealed this 22nd. day of September, A. D. 1936.

SEAL. I 1 HENRY VAN ARSDALE,

Acting Commissioner of Patents.

